Dual Catalyst System for Producing High Density Polyethylenes With Long Chain Branching

ABSTRACT

Disclosed herein are ethylene-based polymers generally characterized by a melt index of less than 1 g/10 min, a density from 0.93 to 0.965 g/cm3, a CY-a parameter at 190° C. of less than 0.2, an average number of short chain branches per 1000 total carbon atoms of the polymer in a molecular weight range of 400,000 to 600,000 g/mol that is greater than that in a molecular weight range of 40,000 to 60,000 g/mol, and an average number of long chain branches per 1000 total carbon atoms of the polymer in a molecular weight range of 400,000 to 600,000 g/mol that is greater than that in a molecular weight range of 4,000,000 to 6,000,000 g/mol. The ethylene polymers can be used to fabricate pipes, blown films, and blow molded products, and the ethylene polymers can be produced with a dual catalyst system containing a single atom bridged or two carbon atom bridged metallocene compound with two indenyl groups or an indenyl group and a cyclopentadienyl group, and a single atom bridged metallocene compound with a fluorenyl group and a cyclopentadienyl group with an alkenyl substituent.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andcopolymer and linear low density polyethylene (LLDPE) copolymer can beproduced using various combinations of catalyst systems andpolymerization processes. Ziegler-Nana and chromium-based catalystsystems can, for example, produce ethylene polymers having goodextrusion processability, polymer melt strength in pipe and blow moldingapplications, and bubble stability in blown film applications, typicallydue to their broad molecular weight distribution (MWD). Metallocenebased catalyst systems can, for example, produce ethylene polymershaving excellent impact and toughness properties, but often at theexpense of poor extrusion processability, melt strength, and bubblestability.

In some end-uses, such as pipe extrusion, blow molding, and blown film,it can be beneficial to have the properties of a metallocene-catalyzedmedium density or high density copolymer, but with improvedprocessability, shear thinning, melt strength, and bubble stability.Accordingly, it is to these ends that the present invention is generallydirected.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to ethylene polymers (e.g.,ethylene/α-olefin copolymers) characterized by a melt index of less thanor equal to about 1 g/10 min, a density in a range from about 0.93 toabout 0.965 g/cm³, a CY-a parameter at 190° C. of less than or equal toabout 0.2, an average number of short chain branches (SCB's) per 1000total carbon atoms of the polymer in a molecular weight range of 400,000to 600,000 g/mol that is greater (e.g., at least 25% greater, or atleast 100% greater) than that in a molecular weight range of 40,000 to60,000 g/mol, and an average number of long chain branches (LCB's) per1000 total carbon atoms of the polymer in a molecular weight range of400,000 to 600,000 g/mol that is greater (e.g., at least 50% greater, orat least 200% greater) than that in a molecular weight range of4,000,000 to 6,000,000 g/mol. Beneficially, there are typically moreSCB's present in the higher molecular weight portions of the ethylenepolymer than in the lower molecular weight portions, and moreover, asignificant amount of the LCB's are present in these higher molecularweight portions of the ethylene polymer, but not in the very highmolecular weight fraction (often referred to as the high molecularweight tail of the molecular weight distribution). The ethylene polymersdisclosed herein can be used to produce various articles of manufacture,such as films (e.g., blown films), sheets, pipes, geomembranes, and blowmolded products.

Another aspect of this invention is directed to a dual catalyst system,and in this aspect, the dual catalyst system can comprise catalystcomponent I comprising a single atom bridged or two carbon atom bridgedmetallocene compound with two indenyl groups or an indenyl group and acyclopentadienyl group, catalyst component II comprising a single atombridged metallocene compound with a fluorenyl group and acyclopentadienyl group with an alkenyl substituent, an activator, andoptionally, a co-catalyst.

In yet another aspect, an olefin polymerization process is provided, andin this aspect, the process can comprising contacting any catalystcomposition disclosed herein with an olefin monomer and an optionalolefin comonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer. For instance, the olefinmonomer can be ethylene, and the olefin comonomer can be 1-butene,1-hexene, 1-octene, or a mixture thereof.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a dynamic rheology plot (viscosity versus shear rate) at190° C. for the polymers of Examples 37-38, 41, 65, and 76.

FIG. 2 presents a plot of the molecular weight distributions of thepolymers of Examples 37-38, 41, 65, and 76.

FIG. 3 presents a plot of the long chain branch distribution across themolecular weight distribution of the polymer of Example 41.

FIG. 4 presents a plot of the long chain branch distribution across themolecular weight distribution of the polymer of Example 60.

FIG. 5 presents a plot of the long chain branch distribution across themolecular weight distribution of the polymer of Example 61.

FIG. 6 presents a plot of the short chain branch distribution across themolecular weight distribution of the polymer of Example 41.

FIG. 7 presents a plot of the short chain branch distribution across themolecular weight distribution of the polymer of Example 60.

FIG. 8 presents a plot of the short chain branch distribution across themolecular weight distribution of the polymer of Example 61.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter are described such that, withinparticular aspects, a combination of different features can beenvisioned. For each and every aspect and/or feature disclosed herein,all combinations that do not detrimentally affect the designs,compositions, processes, and/or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect and/or feature disclosed herein can be combined to describeinventive features consistent with the present disclosure.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodsalso can “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; catalyst component I, catalyst component II, an activator, and aco-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and the like, as well as alloysand blends thereof. The term “polymer” also includes impact, block,graft, random, and alternating copolymers. A copolymer is derived froman olefin monomer and one olefin comonomer, while a terpolymer isderived from an olefin monomer and two olefin comonomers. Accordingly,“polymer” encompasses copolymers and terpolymers derived from any olefinmonomer and comonomer(s) disclosed herein. Similarly, the scope of theterm “polymerization” includes homopolymerization, copolymerization, andterpolymerization. Therefore, an ethylene polymer would include ethylenehomopolymers, ethylene copolymers (e.g., ethylene/α-olefin copolymers),ethylene terpolymers, and the like, as well as blends or mixturesthereof. Thus, an ethylene polymer encompasses polymers often referredto in the art as LLDPE (linear low density polyethylene) and HDPE (highdensity polyethylene). As an example, an olefin copolymer, such as anethylene copolymer, can be derived from ethylene and a comonomer, suchas 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer wereethylene and 1-hexene, respectively, the resulting polymer could becategorized an as ethylene/1-hexene copolymer. The term “polymer” alsoincludes all possible geometrical configurations, unless statedotherwise, and such configurations can include isotactic, syndiotactic,and random symmetries. Moreover, unless stated otherwise, the term“polymer” also is meant to include all molecular weight polymers, and isinclusive of lower molecular weight polymers.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBronsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands can include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst,” in much the sameway the term “co-catalyst” is used herein to refer to, for example, anorganoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, catalystcomponent I, catalyst component II, or the activator (e.g.,activator-support), after combining these components. Therefore, theterms “catalyst composition,” “catalyst mixture,” “catalyst system,” andthe like, encompass the initial starting components of the composition,as well as whatever product(s) may result from contacting these initialstarting components, and this is inclusive of both heterogeneous andhomogenous catalyst systems or compositions. The terms “catalystcomposition,” “catalyst mixture,” “catalyst system,” and the like, canbe used interchangeably throughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time, unless otherwise specified. Forexample, the components can be contacted by blending or mixing. Further,contacting of any component can occur in the presence or absence of anyother component of the compositions described herein. Combiningadditional materials or components can be done by any suitable method.Further, the term “contact product” includes mixtures, blends,solutions, slurries, reaction products, and the like, or combinationsthereof. Although “contact product” can include reaction products, it isnot required for the respective components to react with one another.Similarly, the term “contacting” is used herein to refer to materialswhich can be blended, mixed, slurried, dissolved, reacted, treated, orotherwise combined in some other manner.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices, and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

Several types of ranges are disclosed in the present invention. When arange of any type is disclosed or claimed, the intent is to disclose orclaim individually each possible number that such a range couldreasonably encompass, including end points of the range as well as anysub-ranges and combinations of sub-ranges encompassed therein. Forexample, when a chemical moiety having a certain number of carbon atomsis disclosed or claimed, the intent is to disclose or claim individuallyevery possible number that such a range could encompass, consistent withthe disclosure herein. For example, the disclosure that a moiety is a C₁to C₁₈ hydrocarbyl group, or in alternative language, a hydrocarbylgroup having from 1 to 18 carbon atoms, as used herein, refers to amoiety that can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, or 18 carbon atoms, as well as any range between these twonumbers (for example, a C₁ to C₈ hydrocarbyl group), and also includingany combination of ranges between these two numbers (for example, a C₂to C₄ and a C₁₂ to C₁₆ hydrocarbyl group).

Similarly, another representative example follows for the ratio of Mw/Mnof an ethylene polymer consistent with aspects of this invention. By adisclosure that the ratio of Mw/Mn can be in a range from about 5 toabout 15, the intent is to recite that the ratio of Mw/Mn can be anyratio in the range and, for example, can be equal to about 5, about 6,about 7, about 8, about 9, about 10, about 11, about 12, about 13, about14, or about 15. Additionally, the ratio of Mw/Mn can be within anyrange from about 5 to about 15 (for example, from about 6 to about 15),and this also includes any combination of ranges between about 5 andabout 15 (for example, the Mw/Mn ratio can be in a range from about 6 toabout 9, or from about 11 to about 14). Further, in all instances, where“about” a particular value is disclosed, then that value itself isdisclosed. Thus, the disclosure that the ratio of Mw/Mn can be fromabout 5 to about 15 also discloses a ratio of Mw/Mn from 5 to 15 (forexample, from 6 to 15), and this also includes any combination of rangesbetween 5 and 15 (for example, the Mw/Mn ratio can be in a range from 6to 9, or from 11 to 14). Likewise, all other ranges disclosed hereinshould be interpreted in a manner similar to these examples.

The term “about” means that amounts, sizes, formulations, parameters,and other quantities and characteristics are not and need not be exact,but can be approximate and/or larger or smaller, as desired, reflectingtolerances, conversion factors, rounding off, measurement errors, andthe like, and other factors known to those of skill in the art. Ingeneral, an amount, size, formulation, parameter or other quantity orcharacteristic is “about” or “approximate” whether or not expresslystated to be such. The term “about” also encompasses amounts that differdue to different equilibrium conditions for a composition resulting froma particular initial mixture. Whether or not modified by the term“about,” the claims include equivalents to the quantities. The term“about” can mean within 10% of the reported numerical value, preferablywithin 5% of the reported numerical value.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to medium and high densityethylene-based polymers having excellent strength and toughnessproperties, but with improved processability, shear thinning, meltstrength, and bubble stability. Articles produced from theseethylene-based polymers can include pipes, blow molded products, andblown films.

Advantageously, the ethylene polymers disclosed herein can have moreshort chain branches (SCB's) present in the higher molecular weightportions (e.g., 400,000-600,000 g/mol range) of the ethylene polymerthan in the lower molecular weight portions (e.g., 40,000-60,000 g/molrange). Moreover, in the same general high molecular weight range(400,000-600,000 g/mol), the ethylene polymer also can have more longchain branches (LCB's) per 1000 total carbon atoms than in the very highmolecular weight tail (e.g., 4,000,000-6,000,000 g/mol range). Thus,relatively high amounts of both short chain branching and long chainbranching are concentrated in a particular high molecular weight portionof these ethylene polymers.

These ethylene polymers can be produced, for example, with a dualmetallocene catalyst system in a single reactor. It was found that usinga first metallocene catalyst that preferentially produces lowermolecular weight polyethylene with relatively high LCB content incombination with a second metallocene catalyst that preferentiallyproduces higher molecular weight polyethylene with relatively highcomonomer incorporation can result in the unique combination of polymerproperties described herein.

Ethylene Polymers

Generally, the polymers disclosed herein are ethylene-based polymers, orethylene polymers, encompassing homopolymers of ethylene as well ascopolymers, terpolymers, etc., of ethylene and at least one olefincomonomer. Comonomers that can be copolymerized with ethylene often canhave from 3 to 20 carbon atoms in their molecular chain. For example,typical comonomers can include, but are not limited to, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the like, orcombinations thereof. In an aspect, the olefin comonomer can comprise aC₃-C₁₈ olefin; alternatively, the olefin comonomer can comprise a C₃-C₁₀olefin; alternatively, the olefin comonomer can comprise a C₄-C₁₀olefin; alternatively, the olefin comonomer can comprise a C₃-C₁₀α-olefin; alternatively, the olefin comonomer can comprise a C₄-C₁₀α-olefin; alternatively, the olefin comonomer can comprise 1-butene,1-hexene, 1-octene, or any combination thereof; or alternatively, thecomonomer can comprise 1-hexene. Typically, the amount of the comonomer,based on the total weight of monomer (ethylene) and comonomer, can be ina range from about 0.01 to about 20 wt. %, from about 0.1 to about 10wt. %, from about 0.5 to about 15 wt. %, from about 0.5 to about 8 wt.%, or from about 1 to about 15 wt. %.

In one aspect, the ethylene polymer of this invention can comprise anethylene/α-olefin copolymer, while in another aspect, the ethylenepolymer can comprise an ethylene homopolymer, and in yet another aspect,the ethylene polymer of this invention can comprise an ethylene/α-olefincopolymer and an ethylene homopolymer. For example, the ethylene polymercan comprise an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, an ethylene/1-octene copolymer, an ethylene homopolymer, orany combination thereof; alternatively, an ethylene/1-butene copolymer,an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or anycombination thereof; or alternatively, an ethylene/1-hexene copolymer.

An illustrative and non-limiting example of an ethylene polymer (e.g.,comprising an ethylene copolymer) of the present invention can have amelt index of less than or equal to about 1 g/10 min, a density in arange from about 0.93 to about 0.965 g/cm³, a CY-a parameter at 190° C.of less than or equal to about 0.2, an average number of short chainbranches (SCB's) per 1000 total carbon atoms of the polymer in amolecular weight range of 400,000 to 600,000 g/mol that is greater thanthat in a molecular weight range of 40,000 to 60,000 g/mol, and anaverage number of long chain branches (LCB's) per 1000 total carbonatoms of the polymer in a molecular weight range of 400,000 to 600,000g/mol that is greater than that in a molecular weight range of 4,000,000to 6,000,000 g/mol. These illustrative and non-limiting examples ofethylene polymers consistent with the present invention also can haveany of the polymer properties listed below and in any combination,unless indicated otherwise.

The densities of ethylene-based polymers disclosed herein often aregreater than or equal to about 0.93 g/cm³, for example, greater than orequal to about 0.935 g/cm³, or greater than or equal to about 0.94g/cm³. Yet, in particular aspects, the density can be in a range fromabout 0.93 to about 0.962 g/cm³, from about 0.93 to about 0.958 g/cm³,from about 0.935 to about 0.965 g/cm³, from about 0.94 to about 0.958g/cm³, or from about 0.95 to about 0.96 g/cm³.

Ethylene polymers described herein often can have a melt index (MI) ofless than or equal to about 1 g/10 min, less than or equal to about 0.7g/10 min, or less than or equal to about 0.5 g/10 min. In furtheraspects, ethylene polymers described herein can have a melt index (MI)of less than or equal to about 0.35 g/10 min, less than or equal toabout 0.25 g/10 min, in a range from about 0.05 to about 1 g/10 min, ina range from about 0.05 to about 0.5 g/10 min, in a range from about0.02 to about 0.7 g/10 min, or in a range from about 0.02 to about 0.35g/10 min.

While not being limited thereto, the ethylene polymer can have a highload melt index (HLMI) in a range from about 2 to about 50 g/10 min;alternatively, from about 3 to about 40 g/10 min; alternatively, fromabout 10 to about 45 g/10 min; or alternatively, from about 12 to about35 g/10 min.

The ratio of high load melt index (HLMI) to melt index (MI), referred toas the ratio of HLMI/MI, is not particularly limited, but typicallyranges from about 60 to about 400, from about 80 to about 400, fromabout 90 to about 300, from about 75 to about 250, or from about 100 toabout 250. In this HLMI/MI ratio, the melt index is not equal to zero.

In an aspect, ethylene polymers described herein can have a ratio ofMw/Mn, or the polydispersity index, in a range from about 3.5 to about18, from about 4 to about 18, from about 4 to about 16, from about 6 toabout 16, from about 5 to about 15, or from about 5 to about 12.Additionally or alternatively, the ethylene polymer can have a ratio ofMz/Mw in a range from about 3.5 to about 10, from about 5 to about 10,from about 4 to about 9, from about 5 to about 9, from about 4 to about8, or from about 5 to about 8.

In an aspect, ethylene polymers described herein can have aweight-average molecular weight (Mw) in a range from about 100,000 toabout 400,000 g/mol, from about 100,000 to about 300,000 g/mol, fromabout 100,000 to about 200,000 g/mol, from about 150,000 to about400,000 g/mol, or from about 150,000 to about 350,000 g/mol.Additionally or alternatively, the ethylene polymer can have anumber-average molecular weight (Mn) in a range from about 10,000 toabout 100,000 g/mol, from about 10,000 to about 50,000 g/mol, from about10,000 to about 40,000 g/mol, from about 10,000 to about 30,000 g/mol,from about 12,000 to about 40,000 g/mol, or from about 12,000 to about28,000 g/mol. Additionally or alternatively, the ethylene polymer canhave a z-average molecular weight (Mz) in a range from about 500,000 toabout 2,500,000 g/mol, from about 600,000 to about 2,000,000 g/mol, fromabout 750,000 to about 2,500,000 g/mol, from about 750,000 to about2,000,000 g/mol, from about 750,000 to about 1,750,000 g/mol, or fromabout 750,000 to about 1,500,000 g/mol.

While not limited thereto, ethylene polymers described herein can have azero-shear viscosity at 190° C. in a range from about 1×10⁵ to about1×10¹⁷ Pa-sec, from about 1×10⁶ to about 1×10¹⁶ Pa-sec, or from about1×10⁷ to about 1×10¹³ Pa-sec. Moreover, these ethylene polymers can havea CY-a parameter of less than or equal to about 0.2, such as from about0.02 to about 0.2, from about 0.02 to about 0.18, from about 0.02 toabout 0.10, from about 0.03 to about 0.2, from about 0.03 to about 0.15,from about 0.04 to about 0.16, or from about 0.04 to about 0.12. Thezero-shear viscosity and the CY-a parameter are determined fromviscosity data measured at 190° C. and using the Carreau-Yasuda (CY)empirical model as described herein.

The average number of long chain branches (LCB's) per 1000 total carbonatoms of the ethylene polymer in a molecular weight range of 400,000 to600,000 g/mol is greater (by any amount disclosed herein, e.g., at least50%, at least 75%, at least 100%, at least 200%, or at least 400%, andoften up to 1000-1500%, or more) than the average number of LCB's per1000 total carbon atoms in a molecular weight range of 4,000,000 to6,000,000 g/mol. In some aspects, the average number of long chainbranches (LCB's) per 1000 total carbon atoms of the ethylene polymer ina molecular weight range of 400,000 to 600,000 g/mol can be at least 50%greater (or at least 75% greater, or at least 100% greater, or at least200% greater, or at least 400% greater, or at least 500% greater, andoften up to 1000-1500% greater) than that in a molecular weight range of4,000,000 to 6,000,000 g/mol. All average numbers of LCB's disclosedherein are number-average numbers.

The average number of long chain branches (LCB's) per 1000 total carbonatoms of the ethylene polymer in the molecular weight range of 400,000to 600,000 g/mol is not particularly limited, but often falls within arange from about 0.015 to about 0.085; alternatively, from about 0.02 toabout 0.07; alternatively, from about 0.03 to about 0.07; alternatively,from about 0.02 to about 0.06; or alternatively, from about 0.03 toabout 0.06.

In the overall polymer (using the Janzen-Colby model), the ethylenepolymers typically have levels of long chain branches (LCB's) in a rangefrom about 0.01 to about 0.08 LCB's, from about 0.01 to about 0.06LCB's, from about 0.02 to about 0.06 LCB's, from about 0.02 to about0.05, or from about 0.025 to about 0.045 LCB's, per 1000 total carbonatoms.

Moreover, the ethylene polymers typically have a reverse short chainbranching distribution (SCB content increases with molecular weight).This SCBD feature is quantified herein by the average number of shortchain branches (SCB's) per 1000 total carbon atoms of the ethylenepolymer in a molecular weight range of 400,000 to 600,000 g/mol that isgreater than that in a molecular weight range of 40,000 to 60,000 g/mol.In some aspects, the average number of short chain branches (SCB's) per1000 total carbon atoms of the ethylene polymer in a molecular weightrange of 400,000 to 600,000 g/mol is at least 25% greater (or at least50% greater, or at least 75% greater, or at least 100% greater, or atleast 125% greater, or at least 150% greater, and often up to 250-500%greater) than that in a molecular weight range of 40,000 to 60,000g/mol. All average numbers of SCB's disclosed herein are number-averagenumbers.

A reverse SCBD can be further characterized by the number of short chainbranches (SCB's) per 1000 total carbon atoms of the ethylene polymer atthe weight-average molecular weight (M_(w)) that is greater than at thenumber-average molecular weight (M_(n)), and/or the number of SCB's per1000 total carbon atoms of the ethylene polymer at the z-averagemolecular weight (M_(z)) that is greater than at M_(w), and/or thenumber of SCB's per 1000 total carbon atoms of the ethylene polymer atM_(z) that is greater than at M_(n).

In an aspect, the ethylene polymer described herein can be a reactorproduct (e.g., a single reactor product), for example, not apost-reactor blend of two polymers, for instance, having differentmolecular weight characteristics. As one of skill in the art wouldreadily recognize, physical blends of two different polymer resins canbe made, but this necessitates additional processing and complexity notrequired for a reactor product.

Articles and Products

Articles of manufacture can be formed from, and/or can comprise, theolefin polymers (e.g., ethylene polymers) of this invention and,accordingly, are encompassed herein. For example, articles which cancomprise the polymers of this invention can include, but are not limitedto, an agricultural film, an automobile part, a bottle, a container forchemicals, a drum, a fiber or fabric, a food packaging film orcontainer, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, an outdoor storage product, outdoor play equipment, a pipe, asheet or tape, a toy, or a traffic barrier, and the like. Variousprocesses can be employed to form these articles. Non-limiting examplesof these processes include injection molding, blow molding, rotationalmolding, film extrusion, sheet extrusion, profile extrusion,thermoforming, and the like. Additionally, additives and modifiers oftenare added to these polymers in order to provide beneficial polymerprocessing or end-use product attributes. Such processes and materialsare described in Modern Plastics Encyclopedia, Mid-November 1995 Issue,Vol. 72, No. 12; and Film Extrusion Manual—Process, Materials,Properties, TAPPI Press, 1992; the disclosures of which are incorporatedherein by reference in their entirety. In some aspects of thisinvention, an article of manufacture can comprise any of olefin polymers(or ethylene polymers) described herein, and the article of manufacturecan be or can comprise a blown film, a pipe, or a blow molded product.

Also contemplated herein is a method for forming or preparing an articleof manufacture comprising any polymer disclosed herein. For instance, amethod can comprise (i) contacting a catalyst composition with an olefinmonomer (e.g., ethylene) and an optional olefin comonomer underpolymerization conditions in a polymerization reactor system to producean olefin polymer (e.g., an ethylene polymer), wherein the catalystcomposition can comprise catalyst component I, catalyst component II, anactivator (e.g., an activator-support comprising a solid oxide treatedwith an electron-withdrawing anion), and an optional co-catalyst (e.g.,an organoaluminum compound); and (ii) forming an article of manufacturecomprising the olefin polymer (or ethylene polymer). The forming stepcan comprise blending, melt processing, extruding, molding, orthermoforming, and the like, including combinations thereof.

Any suitable additive can be combined with the polymer in the meltprocessing step (extrusion step), such as antioxidants, acid scavengers,antiblock additives, slip additives, colorants, fillers, processingaids, UV inhibitors, and the like, as well as combinations thereof.

Catalyst Systems and Polymerization Processes

In accordance with aspects of the present invention, the olefin polymer(e.g., the ethylene polymer) can be produced using a dual catalystsystem. In these aspects, catalyst component I can comprise any suitablesingle atom bridged or two carbon atom bridged metallocene compound withtwo indenyl groups or an indenyl group and a cyclopentadienyl group, orany single atom bridged or two carbon atom bridged metallocene compoundwith two indenyl groups or an indenyl group and a cyclopentadienyl groupdisclosed herein. Catalyst component II can comprise any suitable singleatom bridged metallocene compound with a fluorenyl group and acyclopentadienyl group with an alkenyl substituent, or any single atombridged metallocene compound with a fluorenyl group and acyclopentadienyl group with an alkenyl substituent disclosed herein. Thecatalyst system also can comprise any suitable activator or anyactivator disclosed herein, and optionally, any suitable co-catalyst orany co-catalyst disclosed herein.

Referring first to catalyst component II, which can comprise a singleatom bridged metallocene compound with a fluorenyl group and acyclopentadienyl group with an alkenyl substituent. In one aspect, thefluorenyl group can be substituted, while in another aspect, thefluorenyl group can be unsubstituted. Additionally, the bridgedmetallocene compound of catalyst component II can contain zirconium,hafnium, or titanium. Further, the single atom bridge can be a singlecarbon atom or a single silicon atom, although not limited thereto. Insome aspects, this bridging atom can have two substituents independentlyselected from H or any C₁ to C₁₈ hydrocarbyl group disclosed herein(e.g., one substituent, or both substituents, can be a phenyl group).The alkenyl substituent on the cyclopentadienyl group can be anysuitable alkenyl group, such as a C₃ to C₁₈ alkenyl group, or a C₃ to C₈terminal alkenyl group.

Catalyst component II can comprise, in particular aspects of thisinvention, a bridged metallocene compound having formula (II):

Within formula (II), M, Cp, R^(X), R^(Y), E, and each X are independentelements of the bridged metallocene compound. Accordingly, the bridgedmetallocene compound having formula (II) can be described using anycombination of M, Cp, R^(X), R^(Y), E, and X disclosed herein.

In accordance with aspects of this invention, the metal in formula (II),M, can be Ti, Zr, or Hf In one aspect, for instance, M can be Zr or Hf,while in another aspect, M can be Ti; alternatively, M can be Zr; oralternatively, M can be Hf.

Each X in formula (II) independently can be a monoanionic ligand. Insome aspects, suitable monoanionic ligands can include, but are notlimited to, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, aC₁ to C₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁to C₃₆ hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,—OBR¹ ₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand. In addition to representative selections for each Xthat are disclosed herein, additional suitable hydrocarbyl groups,hydrocarboxy groups, hydrocarbylaminyl groups, hydrocarbylsilyl groups,and hydrocarbylaminylsilyl groups are disclosed, for example, in U.S.Pat. No. 9,758,600, incorporated herein by reference in its entirety.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR¹ ₂, or OSO₂R¹, wherein R¹is a C₁ to C₁₈ hydrocarbyl group. In another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group, aC₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, a C₁to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ to C₁₂ hydrocarbyl group. Inanother aspect, each X independently can be H, BH₄, a halide, a C₁ toC₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ to C₁₀hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ to C₁₀hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₁₀ hydrocarbyl group. In yet another aspect, each X independently canbe H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, a C₁ to C₈hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR¹ ₂,or OSO₂R¹, wherein R¹ is a C₁ to C₈ hydrocarbyl group. In still anotheraspect, each X independently can be a halide or a C₁ to C₁₈ hydrocarbylgroup. For example, each X can be Cl.

In one aspect, each X independently can be H, BH4, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, each X can be H;alternatively, F; alternatively, Cl; alternatively, Br; alternatively,I; alternatively, BH₄; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, a C₁ toC₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₁₈ hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C_(36,) a C₁ to C_(18,) a C₁ toC_(12,) or a C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (II), Cp can be a cyclopentadienyl group with an alkenylsubstituent. In some aspects, Cp can contain no additional substituents,other than the alkenyl substituent. In other aspects, Cp can be furthersubstituted with one substituent, two substituents, and so forth. Ifpresent, each additional substituent on Cp independently can be H, ahalide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. Importantly, each additional substituent on Cpcan be either the same or a different substituent group. Moreover, eachadditional substituent can be at any position on the cyclopentadienylring structure that conforms with the rules of chemical valence. Ingeneral, any additional substituent on Cp, independently, can be H orany halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenatedhydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆hydrocarbylsilyl group described herein. In addition to representativesubstituents that are disclosed herein, additional suitable hydrocarbylgroups, halogenated hydrocarbyl groups, hydrocarboxy groups, andhydrocarbylsilyl groups are disclosed, for example, in U.S. Pat. No.9,758,600, incorporated herein by reference in its entirety.

In one aspect, for example, each additional substituent on Cpindependently can be a C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂hydrocarbylsilyl group. In another aspect, each additional substituenton Cp independently can be a C₁ to C₈ alkyl group or a C₃ to C₈ alkenylgroup. In yet another aspect, each additional substituent on Cpindependently can be H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, a decenyl group, aphenyl group, a tolyl group, a benzyl group, a naphthyl group, atrimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group,or an allyldimethylsilyl group.

Similarly, R^(X) and R^(Y) in formula (II) independently can be H or anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl groupdisclosed herein. In one aspect, for example, R^(X) and R^(Y)independently can be H or a C₁ to C₁₂ hydrocarbyl group. In anotheraspect, R^(X) and R^(Y) independently can be a C₁ to C₁₀ hydrocarbylgroup or, alternatively, a C₁ to C₆ alkyl group. In yet another aspect,R^(X) and R^(Y) independently can be H, Cl, CF₃, a methyl group, anethyl group, a propyl group, a butyl group (e.g., t-Bu), a pentyl group,a hexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a tolyl group, a benzyl group, anaphthyl group, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group, and the like. Instill another aspect, R^(X) and R^(Y) independently can be a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a tolyl group, or a benzylgroup.

Bridging group E in formula (II) can be a bridging group having theformula >E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A)and R^(B) independently can be H or a C₁ to C₁₈ hydrocarbyl group. Insome aspects of this invention, R^(A) and R^(B) independently can be aC₁ to C₁₂ hydrocarbyl group; alternatively, R^(A) and R^(B)independently can be a C₁ to C₈ hydrocarbyl group; alternatively, R^(A)and R^(B) independently can be a phenyl group, a C₁ to C₈ alkyl group,or a C₃ to C₈ alkenyl group; alternatively, R^(A) and R^(B)independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, acyclohexylphenyl group, a naphthyl group, a tolyl group, or a benzylgroup; or alternatively, R^(A) and R^(B) independently can be a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a phenyl group, or a benzyl group. In these and otheraspects, R^(A) and R^(B) can be either the same or different.

Illustrative and non-limiting examples of bridged metallocene compoundshaving formula (II) and/or suitable for use as catalyst component II caninclude the following compounds (Me=methyl, Ph=phenyl; t-Bu=tert-butyl):

and the like, as well as combinations thereof.

Catalyst component II is not limited solely to the bridged metallocenecompounds such as described above. Other suitable bridged metallocenecompounds are disclosed in U.S. Pat. Nos. 7,026,494, 7,041,617,7,226,886, 7,312,283, 7,517,939, and 7,619,047, which are incorporatedherein by reference in their entirety.

Catalyst component I can comprise, in particular aspects of thisinvention, a single atom bridged or two carbon atom bridged metallocenecompound with two indenyl groups or an indenyl group and acyclopentadienyl group. Independently, the cyclopentadienyl group andthe indenyl group can be substituted or unsubstituted. Often, catalystcomponent I contains zirconium or titanium, and more often, catalystcomponent I can be a zirconium-based metallocene compound.

In one aspect, catalyst component I has two indenyl groups, such as twounsubstituted indenyl groups. If the metallocene compound is a singleatom bridged metallocene compound, the bridging atom can be carbon orsilicon. Similar to bridging group E in formula (II), the carbon orsilicon bridging atom can have two substituents independently selectedfrom H or a C₁ to C₁₈ hydrocarbyl group, or from H or a C₁ to C₈hydrocarbyl group; alternatively, two substituents independentlyselected from a C₁ to C₆ alkyl group; or alternatively, two substituentsindependently selected from a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a phenylgroup, a cyclohexylphenyl group, a naphthyl group, a tolyl group, or abenzyl group. The two substituents can be either the same or different.

If the metallocene compound is a two carbon atom bridged metallocenecompound, the two carbon atom bridge can be substituted orunsubstituted. For instance, the bridging group can have the formula—CR^(C)R^(D)—CR^(E)R^(F)—, wherein R^(C), R^(D), R^(E), and R^(F)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein. For instance, R^(C), R^(D), R^(E), and R^(F) independently canbe H or a C₁ to C₆ alkyl group, or alternatively, H or a methyl group.

In another aspect, catalyst component I has an indenyl group and acyclopentadienyl group. The indenyl group and the cyclopentadienylgroup, independently, can be substituted or unsubstituted. In someaspects, at least one of the indenyl group and the cyclopentadienylgroup is substituted, and the substituent (or substituents) can be anysubstituent disclosed hereinabove as a substituent for Cp in formula(II). Thus, each substituent, independently, can be a C₁ to C₁₂hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group, oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group.

As above, if a single carbon or silicon atom is the bridging atombetween the indenyl group and the cyclopentadienyl group, the carbon orsilicon bridging atom—similar to bridging group E in formula (II)—canhave two substituents independently selected from H or a C₁ to C₁₈hydrocarbyl group, two substituents independently selected from H or aC₁ to C₈ hydrocarbyl group, or two substituents independently selectedfrom a C₁ to C₆ alkyl group. The two substituents can be either the sameor different.

Illustrative and non-limiting examples of metallocene compounds suitablefor use as catalyst component I can include the following compounds:

and the like, as well as combinations thereof.

Catalyst component I is not limited solely to the bridged metallocenecompounds such as described above. Other suitable metallocene compoundsare disclosed in U.S. Pat. Nos. 8,288,487 and 8,426,538, which areincorporated herein by reference in their entirety.

According to an aspect of this invention, the weight ratio of catalystcomponent I to catalyst component II in the catalyst composition can bein a range from about 10:1 to about 1:10, from about 8:1 to about 1:8,from about 5:1 to about 1:5, from about 4:1 to about 1:4, from about 3:1to about 1:3; from about 2:1 to about 1:2, from about 1.5:1 to about1:1.5, from about 1.25:1 to about 1:1.25, or from about 1.1:1 to about1:1.1. In another aspect, catalyst component I is the major component ofthe catalyst composition, and in such aspects, the weight ratio ofcatalyst component Ito catalyst component II in the catalyst compositioncan be in a range from about 10:1 to about 1:1, from about 8:1 to about1.5:1, from about 5:1 to about 1.5:1, or from about 5:1 to about 2:1.

Additionally, the dual catalyst system contains an activator. Forexample, the catalyst system can contain an activator-support, analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, and the like, or any combination thereof. Thecatalyst system can contain one or more than one activator.

In one aspect, the catalyst system can comprise an aluminoxane compound,an organoboron or organoborate compound, an ionizing ionic compound, andthe like, or a combination thereof. Examples of such activators aredisclosed in, for instance, U.S. Pat. Nos. 3,242,099, 4,794,096,4,808,561, 5,576,259, 5,807,938, 5,919,983, and 8,114,946, thedisclosures of which are incorporated herein by reference in theirentirety. In another aspect, the catalyst system can comprise analuminoxane compound. In yet another aspect, the catalyst system cancomprise an organoboron or organoborate compound. In still anotheraspect, the catalyst system can comprise an ionizing ionic compound.

In other aspects, the catalyst system can comprise an activator-support,for example, an activator-support comprising a solid oxide treated withan electron-withdrawing anion. Examples of such materials are disclosedin, for instance, U.S. Pat. Nos. 7,294,599, 7,601,665, 7,884,163,8,309,485, 8,623,973, and 9,023,959, which are incorporated herein byreference in their entirety. For instance, the activator-support cancomprise fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluorided-chloridedsilica-coated alumina, fluorided silica-coated alumina, sulfatedsilica-coated alumina, or phosphated silica-coated alumina, and thelike, as well as any combination thereof. In some aspects, theactivator-support can comprise a fluorided solid oxide and/or a sulfatedsolid oxide.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metal ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, etc.) are wellknown to those of skill in the art.

The present invention can employ catalyst compositions containingcatalyst component I, catalyst component II, an activator (one or morethan one), and optionally, a co-catalyst. When present, the co-catalystcan include, but is not limited to, metal alkyl, or organometal,co-catalysts, with the metal encompassing boron, aluminum, zinc, and thelike. Optionally, the catalyst systems provided herein can comprise aco-catalyst, or a combination of co-catalysts. For instance, alkylboron, alkyl aluminum, and alkyl zinc compounds often can be used asco-catalysts in such catalyst systems. Representative boron compoundscan include, but are not limited to, tri-n-butyl borane,tripropylborane, triethylborane, and the like, and this includecombinations of two or more of these materials. While not being limitedthereto, representative aluminum compounds (e.g., organoaluminumcompounds) can include trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, aswell as any combination thereof. Exemplary zinc compounds (e.g.,organozinc compounds) that can be used as co-catalysts can include, butare not limited to, dimethylzinc, diethylzinc, dipropylzinc,dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.Accordingly, in an aspect of this invention, the dual catalystcomposition can comprise catalyst component I, catalyst component II, anactivator-support, and an organoaluminum compound (and/or an organozinccompound).

In another aspect of the present invention, a catalyst composition isprovided which comprises catalyst component I, catalyst component II, anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and/or other similarmaterials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity, discussed herein, in the absence of these additionalmaterials. For example, a catalyst composition of the present inventioncan consist essentially of catalyst component I, catalyst component II,an activator-support, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 250 grams of ethylene polymer (homopolymerand/or copolymer, as the context requires) per gram of activator-supportper hour (abbreviated g/g/hr). In another aspect, the catalyst activitycan be greater than about 350, greater than about 450, or greater thanabout 550 g/g/hr. Yet, in another aspect, the catalyst activity can begreater than about 700 g/g/hr, greater than about 1000 g/g/hr, orgreater than about 2000 g/g/hr, and often as high as 3500-6000 g/g/hr.Illustrative and non-limiting ranges for the catalyst activity includefrom about 500 to about 5000, from about 750 to about 4000, or fromabout 1000 to about 3500 g/g/hr, and the like. These activities aremeasured under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as the diluent, at apolymerization temperature of about 90° C. and a reactor pressure ofabout 400 psig. Moreover, in some aspects, the activator-support cancomprise sulfated alumina, fluorided silica-alumina, or fluoridedsilica-coated alumina, although not limited thereto.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence. In one aspect, for example, thecatalyst composition can be produced by a process comprising contacting,in any order, catalyst component I, catalyst component II, and theactivator, while in another aspect, the catalyst composition can beproduced by a process comprising contacting, in any order, catalystcomponent I, catalyst component II, the activator, and the co-catalyst.

Olefin polymers (e.g., ethylene polymers) can be produced from thedisclosed catalyst systems using any suitable olefin polymerizationprocess using various types of polymerization reactors, polymerizationreactor systems, and polymerization reaction conditions. One such olefinpolymerization process for polymerizing olefins in the presence of acatalyst composition of the present invention can comprise contactingthe catalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition can comprise, as disclosed herein, catalystcomponent I, catalyst component II, an activator, and an optionalco-catalyst. This invention also encompasses any olefin polymers (e.g.,ethylene polymers) produced by any of the polymerization processesdisclosed herein.

As used herein, a “polymerization reactor” includes any polymerizationreactor capable of polymerizing (inclusive of oligomerizing) olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof polymerization reactors include those that can be referred to as abatch reactor, slurry reactor, gas-phase reactor, solution reactor, highpressure reactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof; or alternatively, the polymerization reactorsystem can comprise a slurry reactor, a gas-phase reactor, a solutionreactor, or a combination thereof. The polymerization conditions for thevarious reactor types are well known to those of skill in the art. Gasphase reactors can comprise fluidized bed reactors or staged horizontalreactors. Slurry reactors can comprise vertical or horizontal loops.High pressure reactors can comprise autoclave or tubular reactors.Reactor types can include batch or continuous processes. Continuousprocesses can use intermittent or continuous product discharge.Polymerization reactor systems and processes also can include partial orfull direct recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

A polymerization reactor system can comprise a single reactor ormultiple reactors (2 reactors, more than 2 reactors, etc.) of the sameor different type. For instance, the polymerization reactor system cancomprise a slurry reactor, a gas-phase reactor, a solution reactor, or acombination of two or more of these reactors. Production of polymers inmultiple reactors can include several stages in at least two separatepolymerization reactors interconnected by a transfer device making itpossible to transfer the polymers resulting from the firstpolymerization reactor into the second reactor. The desiredpolymerization conditions in one of the reactors can be different fromthe operating conditions of the other reactor(s). Alternatively,polymerization in multiple reactors can include the manual transfer ofpolymer from one reactor to subsequent reactors for continuedpolymerization. Multiple reactor systems can include any combinationincluding, but not limited to, multiple loop reactors, multiple gasphase reactors, a combination of loop and gas phase reactors, multiplehigh pressure reactors, or a combination of high pressure with loopand/or gas phase reactors. The multiple reactors can be operated inseries, in parallel, or both. Accordingly, the present inventionencompasses polymerization reactor systems comprising a single reactor,comprising two reactors, and comprising more than two reactors. Thepolymerization reactor system can comprise a slurry reactor, a gas-phasereactor, a solution reactor, in certain aspects of this invention, aswell as multi-reactor combinations thereof.

According to one aspect, the polymerization reactor system can compriseat least one loop slurry reactor comprising vertical or horizontalloops. Monomer, diluent, catalyst, and comonomer can be continuously fedto a loop reactor where polymerization occurs. Generally, continuousprocesses can comprise the continuous introduction of monomer/comonomer,a catalyst, and a diluent into a polymerization reactor and thecontinuous removal from this reactor of a suspension comprising polymerparticles and the diluent. Reactor effluent can be flashed to remove thesolid polymer from the liquids that comprise the diluent, monomer and/orcomonomer. Various technologies can be used for this separation stepincluding, but not limited to, flashing that can include any combinationof heat addition and pressure reduction, separation by cyclonic actionin either a cyclone or hydrocyclone, or separation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and8,822,608, each of which is incorporated herein by reference in itsentirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used.

According to yet another aspect, the polymerization reactor system cancomprise at least one gas phase reactor (e.g., a fluidized bed reactor).Such reactor systems can employ a continuous recycle stream containingone or more monomers continuously cycled through a fluidized bed in thepresence of the catalyst under polymerization conditions. A recyclestream can be withdrawn from the fluidized bed and recycled back intothe reactor. Simultaneously, polymer product can be withdrawn from thereactor and new or fresh monomer can be added to replace the polymerizedmonomer. Such gas phase reactors can comprise a process for multi-stepgas-phase polymerization of olefins, in which olefins are polymerized inthe gaseous phase in at least two independent gas-phase polymerizationzones while feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. Representative gasphase reactors are disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790,5,436,304, 7,531,606, and 7,598,327, each of which is incorporated byreference in its entirety herein.

According to still another aspect, the polymerization reactor system cancomprise a high pressure polymerization reactor, e.g., can comprise atubular reactor or an autoclave reactor. Tubular reactors can haveseveral zones where fresh monomer, initiators, or catalysts are added.Monomer can be entrained in an inert gaseous stream and introduced atone zone of the reactor. Initiators, catalysts, and/or catalystcomponents can be entrained in a gaseous stream and introduced atanother zone of the reactor. The gas streams can be intermixed forpolymerization. Heat and pressure can be employed appropriately toobtain optimal polymerization reaction conditions.

According to yet another aspect, the polymerization reactor system cancomprise a solution polymerization reactor wherein the monomer/comonomerare contacted with the catalyst composition by suitable stirring orother means. A carrier comprising an inert organic diluent or excessmonomer can be employed. If desired, the monomer/comonomer can bebrought in the vapor phase into contact with the catalytic reactionproduct, in the presence or absence of liquid material. Thepolymerization zone can be maintained at temperatures and pressures thatwill result in the formation of a solution of the polymer in a reactionmedium. Agitation can be employed to obtain better temperature controland to maintain uniform polymerization mixtures throughout thepolymerization zone. Adequate means are utilized for dissipating theexothermic heat of polymerization.

The polymerization reactor system can further comprise any combinationof at least one raw material feed system, at least one feed system forcatalyst or catalyst components, and/or at least one polymer recoverysystem. Suitable reactor systems can further comprise systems forfeedstock purification, catalyst storage and preparation, extrusion,reactor cooling, polymer recovery, fractionation, recycle, storage,loadout, laboratory analysis, and process control. Depending upon thedesired properties of the olefin polymer, hydrogen can be added to thepolymerization reactor as needed (e.g., continuously, pulsed, etc.).

Polymerization conditions that can be controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. Various polymerization conditions can beheld substantially constant, for example, for the production of aparticular grade of the olefin polymer (or ethylene polymer). A suitablepolymerization temperature can be any temperature below thede-polymerization temperature according to the Gibbs Free energyequation. Typically, this includes from about 60° C. to about 280° C.,for example, or from about 60° C. to about 120° C., depending upon thetype of polymerization reactor(s). In some reactor systems, thepolymerization temperature generally can be within a range from about70° C. to about 100° C., or from about 75° C. to about 95° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) can offer advantages to the polymerizationreaction process.

Olefin monomers that can be employed with catalyst compositions andpolymerization processes of this invention typically can include olefincompounds having from 2 to 30 carbon atoms per molecule and having atleast one olefinic double bond, such as ethylene or propylene. In anaspect, the olefin monomer can comprise a C₂-C₂₀ olefin; alternatively,a C₂-C₂₀ alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, aC₂-C₁₀ alpha-olefin; alternatively, the olefin monomer can compriseethylene; or alternatively, the olefin monomer can comprise propylene(e.g., to produce a polypropylene homopolymer or a propylene-basedcopolymer).

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect, thecomonomer can comprise a C₃-C₁₀ alpha-olefin; alternatively, thecomonomer can comprise 1-butene, 1-pentene, 1-hexene, 1-octene,1-decene, styrene, or any combination thereof; alternatively, thecomonomer can comprise 1-butene, 1-hexene, 1-octene, or any combinationthereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight. Density was determined in grams per cubic centimeter(g/cm³) on a compression molded sample, cooled at 15° C. per hour, andconditioned for 40 hours at room temperature in accordance with ASTMD1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 200 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the standard. The integral table of the standard waspre-determined in a separate experiment with SEC-MALS. Mn is thenumber-average molecular weight, Mw is the weight-average molecularweight, Mz is the z-average molecular weight, and Mp is the peakmolecular weight (location, in molecular weight, of the highest point ofthe molecular weight distribution curve).

Melt rheological characterizations were performed as follows.Small-strain (less than 10%) oscillatory shear measurements wereperformed on an Anton Paar MCR rheometer using parallel-plate geometry.All rheological tests were performed at 190° C. The complex viscosity|η*| versus frequency (ω) data were then curve fitted using the modifiedthree parameter Carreau-Yasuda (CY) empirical model to obtain the zeroshear viscosity—η₀, characteristic viscous relaxation time—τ_(η), andthe breadth parameter—a (CY-a parameter). The simplified Carreau-Yasuda(CY) empirical model is as follows.

${{{\eta^{*}(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$

wherein:

-   -   |η*(ω)|=magnitude of complex shear viscosity;    -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time (Tau(η));    -   a=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters can be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

The long chain branches (LCB's) per 1000 total carbon atoms of theoverall polymer were calculated using the method of Janzen and Colby (J.Mol. Struct., 485/486, 569-584 (1999), incorporated herein by referencein its entirety), from values of zero shear viscosity, η_(o) (determinedfrom the Carreau-Yasuda model, described hereinabove), and measuredvalues of M_(w) obtained using a Dawn EOS multiangle light scatteringdetector (Wyatt). Using the Janzen-Colby method, the polymer of Example41 contained 0.032 LCB's per 1000 total carbon atoms, and isrepresentative of the other ethylene polymers produced in the examples.It is expected that the LCB for the inventive examples will fall in the˜0.01-0.06 range (LCB's per 1000 total carbon atoms).

LCB content and LCB distribution determination was following the methodestablished by Yu, et al (Yu, DesLauriers, Rohlfing, Polymer, 2015, 46,5165-5192, incorporated herein by reference in its entirety). Briefly,in the SEC-MALS system, a DAWN EOS photometer (Wyatt Technology, SantaBarbara, Calif.) was attached to a Waters 150-CV plus GPC system(Milford, Mass.) or a PL-210 GPC system (Polymer Labs, now an Agilentcompany) through a hot-transfer line controlled at 145° C. Degassedmobile phase 1,2,4-trichlorobenzene (TCB) containing 0.5 wt % of BHT(butylated hydroxytoluene) was pumped through an inline filter beforepassing through a SEC column bank. Polymer solutions injected to thesystem were brought downstream to the columns by the mobile phase forfractionation. The fractionated polymers first eluted through the MALSphotometer where light scattering signals were recorded before passingthrough the differential refractive index detector (DRI) or an IR4detector (Polymer Characterization SA, Spain) where their concentrationswere quantified.

The DAWN EOS system was calibrated with neat toluene at room temperatureto convert the measured voltage to intensity of scattered light. Duringthe calibration, toluene was filtered with a 0.02 um filter (Whatman)and directly passed through the flowcell of the EOS system. At roomtemperature, the Rayleigh ratio is given by 1.406×10⁻⁵ cm⁻¹. A narrowpolystyrene (PS) standard (American Polymer Standards) with MW of 30,000g/mol at a concentration about 5-10 mg/mL in TCB was employed tonormalize the system at 145° C. At the given chromatographic conditions,the radius of gyration (R_(g)) of the polystyrene (PS) was estimated tobe 5.6 nm. The differential refractive index detector (DRI) wascalibrated with a known quantity of PE standard. By averaging the totalchromatographic areas of recorded chromatograms for at least fiveinjections, the DRI constant (α_(RI)) was obtained using the equationbelow (equation 1):

$\begin{matrix}{\alpha_{RI} = {\left( \frac{dn}{dc} \right){c/I_{RI}}}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

where I_(RI) is the DRI detector intensity, c is the polymerconcentration, and dn/dc is the refractive index increment of PE in TCBat the measuring temperature.

At a flow rate set at 0.7 mL/min, the mobile phase was eluted throughthree (3) 7.5 mm×300 mm 20 μm mixed A columns (Polymer Labs, now anAgilent company). PE solutions with nominal concentrations of 1.5 mg/mLwere prepared at 150° C. for 4 h. At each chromatographic slice, boththe absolute molecular weight (M) and the root mean square (RMS) radius,aka, radius of gyration, R_(g), were obtained from the Debye plots. Thelinear PE control employed was CPChem Marlex™ HiD9640, a high-density PEwith broad MWD. The refractive index increment dn/dc used in this studywas 0.097 mL/g for PE dissolved in TCB at 135° C.

The Zimm-Stockmayer approach (Zimm, Stockmayer, J. Chem. Phys. 1949, 17,1301, incorporated herein by reference in its entirety) was employed todetermine the amount of LCB in the polyethylene resins. In SEC-MALS,both M and R_(g) were measured simultaneously at each slice of achromatogram. At the same molecular weight, R_(g) of a branched polymeris smaller than that of a linear polymer. The branching index (g_(M))factor is defined as the ratio of the mean square radius of gyration ofthe branched polymer to that of the linear one at the same molecularweight using equation 2,

$\begin{matrix}{g_{M} \equiv \left( \frac{{\langle R_{g}^{2}\rangle}_{b}}{{\langle R_{g}^{2}\rangle}_{l}} \right)_{M}} & {{Equation}\mspace{14mu} 2}\end{matrix}$

where the subscripts b an l represent the branched and linear polymer,respectively.

The weight-average LCB per molecule (B_(3w)) was calculated usingEquation 3 using an in-house software,

$\begin{matrix}{g_{M} = {\frac{6}{B_{3w}}\left\{ {{\frac{1}{2}\left( \frac{2 + B_{3w}}{B_{3w}} \right)^{1/2}{\ln \left\lbrack \frac{\left( {2 + B_{3w}} \right)^{1/2} + \left( B_{3w} \right)^{1/2}}{\left( {2 + B_{3w}} \right)^{1/2} - \left( B_{3w} \right)^{1/2}} \right\rbrack}} - 1} \right\}}} & (3)\end{matrix}$

LCB frequency (λ_(M) _(i) , number of LCB per 1,000 total carbons) wascalculated using equation 4 using the B_(3w) value obtained fromequation 3,

λ_(M) _(i) =1,000×M ₀ ×B _(3w) /M _(i)   (4)

where M₀ is the unit molecular weight of polyethylene, M_(i) is themolecular weight of the i^(th) slice.

Since the presence of SCB in a polymer can affect its R_(g)-MWrelationship, the SCB effect was corrected before using equation 3 and 4for LCB and LCB distribution calculation for PE copolymers. To correctthe SCB effect on the branching index across the MWD, two relationshipsare needed: one is the relationship between the branching-indexcorrection factor (Δg_(M)) and the SCB content (x_(SCB)), and the otheris the relationship between SCB content and molecular weight, both ofwhich were determined experimentally. Mathematically, the product ofthese two relationships gives the branching index correction factor(Δg_(M)) as a function of MW, as shown in equation 5,

$\begin{matrix}{\frac{d\left( {\Delta \; g_{M}} \right)}{d(M)} = {\frac{d\left( x_{SCB} \right)}{d(M)} \times \frac{d\left( {\Delta \; g_{M}} \right)}{d\left( x_{SCB} \right)}}} & (5)\end{matrix}$

where x_(SCB) is the SCB content (i.e., number of SCB per 1,000 totalcarbons) of the copolymer in question.

To establish the relationship between Δg_(M) and x_(SCB), PE standardsthat met the following criteria were used: the standards containessentially no LCB and have flat SCB distribution and known SCBcontents. At least five SCB standards were used for the SCB effectcorrection. The SCB content for these SCB standards ranged from 0 to 34SCB/1,000 total carbon atoms.

Short chain branch content and short chain branching distribution (SCBD)across the molecular weight distribution were determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IR5) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata was obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a HDPE Marlex™ BHB5003 resin (Chevron PhillipsChemical) as the molecular weight standard. The digital signals, on theother hand, go via a USB cable directly to Computer “B” where they arecollected by a LabView data collection software provided by PolymerChar. Chromatographic conditions were set as follows: column oventemperature of 145° C.; flowrate of 1 mL/min; injection volume of 0.4mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell were set at 150° C., while the temperature ofthe electronics of the IR5 detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Fluorided silica-coated alumina activator-supports (FSCA) were preparedas follows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of 300 m²/g, a porevolume of 1.3 mL/g, and an average particle size of 100 microns. Thealumina was first calcined in dry air at about 600° C. for approximately6 hours, cooled to ambient temperature, and then contacted withtetraethylorthosilicate in isopropanol to equal 25 wt. % SiO₂. Afterdrying, the silica-coated alumina was calcined at 600° C. for 3 hours.Fluorided silica-coated alumina (7 wt. % F) was prepared by impregnatingthe calcined silica-coated alumina with an ammonium bifluoride solutionin methanol, drying, and then calcining for 3 hours at 600° C. in dryair. Afterward, the fluorided silica-coated alumina (FSCA) was collectedand stored under dry nitrogen, and was used without exposure to theatmosphere.

Examples 1-76

Comparative Example 76 was a commercially-available chromium-catalyzedHDPE resin from Chevron-Phillips Chemical Company LP, while Examples1-75 were produced as follows. The polymerization experiments ofExamples 1-75 were conducted for 30 min in a one-gallon (3.8-L)stainless-steel autoclave reactor containing two liters of isobutane asdiluent, and hydrogen added from a 325-cc auxiliary vessel. Generally,solutions of the metallocene compounds were prepared by dissolving 20 mgof the respective catalyst component I and catalyst component IImetallocenes in 20 mL of toluene. Under an isobutane purge, 1 mL of TIBA(25% in heptanes), approximately 100-400 mg of FSCA, and the metallocenesolutions were charged to a cold reactor through a charge port. Thereactor was closed, and 2 L of isobutane were added. The reactor wasquickly heated to within 5 degrees of the run temperature and 1-hexene(if used), ethylene, and hydrogen (if used), were then introduced intothe reactor. Ethylene was fed on demand to maintain the target pressure.The reactor was maintained at the desired temperature throughout theexperiment by an automated heating-cooling system. After venting of thereactor, purging, and cooling, the resulting polymer product was driedat 60° C. under reduced pressure. The structures for the metallocenecompounds used in Examples 1-75 are shown below (Ph=phenyl;t-Bu=tert-butyl):

Table I and Table II summarize certain polymerization conditions forExamples 1-66 and Examples 67-75, respectively. Likewise, Table III andTable IV summarize various properties of the polymers of Examples 1-66and Examples 67-75 and Comparative Example 76, respectively. Arepresentative rheology curve (viscosity versus shear rate at 190° C.)for some of the polymers shown in Tables III-IV is presented in FIG. 1,and a representative molecular weight distribution curve (amount ofpolymer versus the logarithm of molecular weight) for some of thepolymers shown in Tables III-IV is presented in FIG. 2. FIG. 1illustrates the dynamic rheology plot for the polymers of Examples37-38, 41, 65, and 76, while FIG. 2 illustrates the molecular weightdistributions for the polymers of Examples 37-38, 41, 65, and 76.

Representative molecular weight distribution and long chain branchdistribution curves for some of the polymers shown in Tables III-IV arepresented in FIGS. 3-5, and representative molecular weight distributionand short chain branch distribution curves for some of the polymersshown in Tables III-IV are presented in FIG. 6-8. FIG. 3 illustrates aplot of the molecular weight distribution and long chain branchdistribution of the polymer of Example 41, while FIG. 4 illustrates aplot of the molecular weight distribution and long chain branchdistribution of the polymer of Example 60, and FIG. 5 illustrates a plotof the molecular weight distribution and long chain branch distributionof the polymer of Example 61. FIG. 6 illustrates a plot of the molecularweight distribution and short chain branch distribution of the polymerof Example 41, while FIG. 7 illustrates a plot of the molecular weightdistribution and short chain branch distribution of the polymer ofExample 60, and FIG. 8 illustrates a plot of the molecular weightdistribution and short chain branch distribution of the polymer ofExample 61. From FIGS. 3-8, Table V summarizes the SCB content and theLCB content of the respective ethylene polymer in certain molecularweight ranges.

From these tables and figures, it is apparent that ethylene polymers(e.g., ethylene/1-hexene copolymers) having a wide range of polymerproperties were produced, such as melt indices of less than 1 g/10 min(or less than 0.5 g/10 min), HLMI/MI ratios in the 10-45 range,densities in the 0.93-0.965 g/cm³ range (or in the 0.93-0.958 g/cm³range), CY-a parameters of less than 0.2 (or in the 0.03-0.15 range),zero-shear viscosities at 190° C. in the 1×10⁶-1×10¹⁶ Pa-sec range,Mw/Mn ratios in the 3.5-18 range (or in the 6 to 16 range), Mz/Mw ratiosin the 3.5-10 range (or in the 5-8 range), Mn values in the10,000-60,000 g/mol range (or in the 10,000-40,000 g/mol range), Mwvalues in the 100,000-400,000 g/mol range (or in the 100,000-300,000g/mol range), and Mz values in the 500,000-2,500,000 g/mol range (or inthe 750,000-1,500,000 g/mol range). In sum, many of the polymers ofExamples 1-75 have polymer properties that would result inprocessability, shear thinning, melt strength, and bubble stabilitycomparable to or better than that of the chromium-based polymer ofExample 76.

The increasing comonomer distribution of the inventive polymers ofExamples 1-75 is illustrated by FIGS. 6-8, which show the molecularweight distributions and short chain branch distributions of thepolymers of Example 41, Example 60, and Example 61, which arerepresentative of the inventive polymers of Examples 1-75. In thesefigures, there are relatively more short chain branches (SCB's) at thehigher molecular weights as compared to the lower molecular weights(assumes 2 methyl chain ends (CE) and the SCB's are per 1000 totalcarbon (TC) atoms of the polymer). In particular, the average number ofSCB's per 1000 total carbon atoms of these polymers in the molecularweight range of 400,000 to 600,000 g/mol was greater than that in themolecular weight range of 40,000 to 60,000 g/mol. The opposite is truefor the chromium-based polymer of Example 76: the average number ofSCB's per 1000 total carbon atoms in the molecular weight range of400,000 to 600,000 g/mol is less than that in the molecular weight rangeof 40,000 to 60,000 g/mol (a decreasing comonomer distribution).

The number-average number of SCB's per 1000 total carbon atoms of therespective polymers in FIGS. 6-8 in the molecular weight range of400,000 to 600,000 g/mol and in the molecular weight range of 40,000 to60,000 g/mol can be calculated based on Equations 6 and 7, respectively,and are summarized in Table V.

$\begin{matrix}{\overset{\_}{x} = \frac{\sum_{{M\; W} = {400\mspace{14mu} {{kg}/{mol}}}}^{{MW} = {600\mspace{14mu} {{kg}/{mol}}}}{{x_{i}\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)}_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}{\sum_{{M\; W} = {400\mspace{14mu} {{kg}/{mol}}}}^{{M\; W} = {600\mspace{14mu} {{kg}/{mol}}}}{\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}} & {{Equation}\mspace{14mu} 6} \\{\mspace{79mu} {\overset{\_}{x} = \frac{\sum_{{M\; W} = {40\mspace{14mu} {{kg}/{mol}}}}^{{MW} = {60\mspace{14mu} {{kg}/{mol}}}}{{x_{i}\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)}_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}{\sum_{{M\; W} = {40\mspace{14mu} {{kg}/{mol}}}}^{{M\; W} = {60\mspace{14mu} {{kg}/{mol}}}}{\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}}} & {{Equation}\mspace{14mu} 7}\end{matrix}$

where x is the number-average SCB number in the respective molecularweight range and x_(i) is SCB at slice i.

As shown in Table V, the number-average number of SCB's per 1000 totalcarbon atoms of the polymers in FIGS. 6-8 in the molecular weight rangeof 400,000 to 600,000 g/mol is ˜122-153% greater than that in themolecular weight range of 40,000 to 60,000 g/mol.

The concentration of long chain branch content in the high molecularweight fraction (but not in the very high molecular weight tail) of theinventive polymers of Examples 1-75 is illustrated by FIGS. 3-5, whichshow the molecular weight distributions and long chain branchdistributions of the polymers of Example 41, Example 60, and Example 61,which are representative of the inventive polymers of Examples 1-75. Inthese figures, the average number of LCB's per 1000 total carbon atomsof the polymers in the molecular weight range of 400,000 to 600,000g/mol was greater than that in the molecular weight range of 4,000,000to 6,000,000 g/mol.

The number-average number of LCB's per 1000 total carbon atoms of therespective polymers in FIGS. 3-5 in the molecular weight range of400,000 to 600,000 g/mol and in the molecular weight range of 4,000,000to 6,000,000 g/mol can be calculated based on Equations 8 and 9,respectively, and are summarized in Table V.

$\begin{matrix}{\overset{\_}{\lambda} = \frac{\sum_{{M\; W} = {400\mspace{14mu} {{kg}/{mol}}}}^{{MW} = {600\mspace{14mu} {{kg}/{mol}}}}{{\lambda_{i}\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)}_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}{\sum_{{M\; W} = {400\mspace{14mu} {{kg}/{mol}}}}^{{M\; W} = {600\mspace{14mu} {{kg}/{mol}}}}{\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}} & {{Equation}\mspace{14mu} 8} \\{\overset{\_}{\lambda} = \frac{\sum_{{M\; W} = {4000\mspace{14mu} {{kg}/{mol}}}}^{{MW} = {6000\mspace{14mu} {{kg}/{mol}}}}{{\lambda_{i}\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)}_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}{\sum_{{M\; W} = {4000\mspace{14mu} {{kg}/{mol}}}}^{{M\; W} = {6000\mspace{14mu} {{kg}/{mol}}}}{\left( \frac{dw}{d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}\left( {d\left( {{Log}\mspace{14mu} M} \right)} \right)_{i}}}} & {{Equation}\mspace{14mu} 9}\end{matrix}$

where λ is the number-average LCB number in the respective molecularweight range and λ_(i) is LCB at slice i.

As shown in Table V, the number-average number of LCB's per 1000 totalcarbon atoms of the polymers in FIGS. 3-5 in the molecular weight rangeof 400,000 to 600,000 g/mol is at least 600% greater than that in themolecular weight range of 4,000,000 to 6,000,000 g/mol. For the examplessummarized in Table V, the number-average number of LCB's per 1000 totalcarbon atoms in the molecular weight range of 400,000 to 600,000 g/molwas in the ˜0.03-0.06 range.

TABLE I Examples 1-66-Polymerization Experiments. MET-2A MET-1A FSCAPressure 1-Hexene H₂ Temperature Polymer Example (mg) (mg) (g) (psig)(g) (ppm) (° C.) (g) 1 0.1 1 0.190 403 5 — 90 241 2 0.2 1 0.188 403 5 —90 159 3 0.3 1 0.176 403 5 — 90 223 4 0.4 1 0.200 403 5 — 90 145 5 0.5 10.192 403 5 — 90 142 6 0.5 1 0.185 403 10 — 90 257 7 0.5 1 0.187 403 5 —95 258 8 1 0.3 0.123 403 5 — 95 140 9 1 0.3 0.109 403 10 — 95 100 10 10.5 0.120 403 5 — 95 135 11 1 0.5 0.128 403 10 — 95 156 12 0.5 0.5 0.119403 5 — 95 120 13 0.5 0.5 0.113 403 10 — 95 87 14 1 0.3 0.117 403 5 — 95201 15 1 0.3 0.114 403 10 — 95 219 16 0.6 0.3 0.102 403 5 — 95 136 170.6 0.3 0.115 403 10 — 95 210 18 1 0.5 0.226 403 5 50 90 200 19 1 0.50.222 403 10 50 90 87 20 1 1 0.198 403 5 50 90 175 21 1 1 0.200 403 1050 90 176 22 1 0.5 0.226 403 5 50 90 190 23 0.5 1 0.190 403 5 50 90 13224 0.5 1 0.200 403 10 50 90 135 25 1 1 0.208 403 2 50 90 253 26 1 10.231 403 4 50 90 279 27 1.5 1 0.208 403 2 50 90 242 28 1.5 1 0.194 4033 — 90 225 29 1.5 1 0.216 403 5 — 90 225 30 0.5 1.2 0.214 403 5 — 90 15331 0.5 1.2 0.195 403 5 150 90 145 32 0.5 1.2 0.191 403 5 250 90 101 330.2 1 0.203 402 10 110 90 235 34 0.2 1 0.202 402 5 110 90 187 35 0.2 10.201 402 10 — 90 366 36 0.2 1 0.202 402 5 — 90 139 37 0.2 1 0.202 402 555 90 180 38 0.2 1 0.201 374 5 55 85 200 39 0.2 1 0.199 402 3 — 90 18940 0.1 1 0.202 402 3 — 90 167 41 0.2 1 0.100 402 3 110 90 77 42 0.1 10.204 402 3 110 90 180 43 0.1 1 0.201 402 5 — 90 177 44 0.1 1 0.198 4021 — 90 204 45 0.1 1 0.203 402 2 — 90 203 46 0.1 1 0.176 402 4 — 90 17647 0.1 1 0.184 374 5 — 85 185 48 0.1 1 0.149 374 3 — 85 149 49 0.1 10.164 374 2 — 85 164 50 0.1 1 0.409 374 2 — 85 409 51 0.4 1 0.202 340 4055 85 67 52 0.4 1 0.201 340 20 110 85 46 53 0.4 1 0.204 402 20 55 90 9554 0.4 1 0.203 374 20 55 85 172 55 0.4 1 0.202 402 40 — 90 178 56 0.4 10.201 430 30 — 95 138 57 0.4 1 0.304 374 20 — 85 125 58 0.4 1 0.300 37440 — 85 87 59 0.4 1 0.300 374 10 — 85 123 60 0.4 1 0.204 374 10 55 85129 61 0.4 1 0.202 374 20 55 85 101 62 0.4 1 0.204 345 10 55 80 102 630.4 1 0.205 345 20 55 80 157 64 0.3 1 0.204 374 10 55 85 177 65 0.3 10.204 345 10 55 80 37 66 0.3 1 0.203 345 20 55 80 94

TABLE II Examples 67-75-Polymerization Experiments. MET-2A MET-1B FSCAPressure 1-Hexene H₂ Temperature Polymer Example (mg) (mg) (g) (psig)(g) (ppm) (° C.) (g) 67 1.2 0.5 0.225 403 5 — 90 111 68 1.2 0.5 0.210403 5 150 90 119 69 1.2 0.5 0.193 403 5 250 90 73 70 1.2 0.5 0.214 403 5350 90 80 71 0.5 1 0.218 403 3 50 90 281 72 0.5 1 0.220 403 10 50 90 15673 0.5 1 0.206 403 5 50 90 156 74 1 1 0.216 403 5 100 90 150 75 1 10.202 403 10 100 90 134

TABLE III Examples 1-66-Polymer Properties. MI HLMI Density η₀ τ_(η) CY-Example (g/10 min) (g/10 min) (g/cc) (Pa-sec) (sec) a  1 0.05 7.7 0.9508.21E+06 3.03E−02 0.074  2 0.01 6.5 0.946 2.33E+10 2.62E+01 0.046  30.03 8.6 0.946 1.30E+09 1.63E+01 0.059  4 — 5.2 0.949 2.96E+12 1.89E+040.041  5 — 3.0 0.948 1.99E+12 1.32E+05 0.046  6 — 3.0 0.940 1.48E+137.54E+05 0.042  7 0.08 9.4 0.946 7.16E+11 1.51E+04 0.044  8 0.03 6.80.940 3.11E+14 2.72E+07 0.038  9 — 2.9 0.934 3.90E+20 5.62E+16 0.036 100.01 3.9 0.940 3.96E+13 6.11E+07 0.048 11 0.05 12 0.936 7.00E+087.01E+02 0.078 12 0 0 0.938 2.05E+09 2.77E+04 0.114 13 0 2.7 0.9331.40E+11 4.26E+06 0.086 14 0.10 2.7 0.934 1.44E+06 6.80E+00 0.417 15 — —0.928 1.24E+06 5.37E+00 0.474 16 — — 0.934 2.25E+06 9.05E+00 0.447 17 —0.1 0.927 1.22E+06 4.89E+00 0.488 18 0.27 14 0.944 1.77E+11 2.47E+010.037 19 1.49 64 0.944 2.85E+05 1.90E−01 0.117 20 0.13 11 0.945 1.16E+124.85E+04 0.043 21 0.07 7.9 0.939 1.30E+09 2.31E+03 0.077 22 0.58 200.945 1.71E+09 1.13E−01 0.043 23 0.07 12 0.946 8.31E+05 1.11E+01 0.25324 — 5.6 0.940 3.08E+06 3.95E+01 0.221 25 0.17 12 0.954 7.59E+113.01E+02 0.037 26 0.22 13 0.950 2.10E+10 9.51E−01 0.039 27 0.30 13 0.9534.75E+07 4.49E−02 0.059 28 0.29 12 0.951 9.20E+07 8.72E−01 0.064 29 0.199.8 0.950 2.82E+08 1.53E+00 0.059 30 — 1.0 0.944 7.71E+08 5.52E+03 0.11831 0.66 55 0.960 2.30E+04 2.93E−01 0.417 32 2.20 124 0.963 4.51E+034.75E−02 0.518 35 0.21 29 0.939 — — — 36 0.12 36 0.940 — — — 37 0.06 200.951 2.88E+12 8.38E+04 0.041 38 0.30 37 0.948 — — — 39 0.16 37 0.942 —— — 40 0.10 10 0.942 2.38E+11 6.24E+01 0.038 41 0.14 35 0.951 3.35E+074.60E+01 0.090 42 3.13 135 — — — — 43 0.12 11 0.941 1.85E+10 2.30E+010.045 44 0.03 7.1 0.947 5.16E+19 3.93E+08 0.021 45 — 6.1 0.943 6.58E+165.81E+08 0.030 46 — 6.5 0.945 1.03E+16 2.95E+07 0.030 47 — 4.7 0.9471.48E+11 1.85E+03 0.047 48 — 2.7 — — — — 49 — 3.0 0.943 3.17E+143.59E+07 0.039 50 — 22 0.950 1.21E+11 1.41E+00 0.035 51 5.28 212 — — — —52 1.07 108 — — — — 53 0.62 79 — — — — 54 0.47 46 — — — — 56 3.40 143 —— — — 57 — 3.2 — 4.26E+14 1.96E+09 0.046 58 0.15 19 — — — — 59 0.01 3.6— 9.30E+15 4.95E+09 0.037 60 0.20 30 0.945 2.80E+08 2.83E+02 0.075 610.20 30 0.933 3.95E+09 2.52E+03 0.061 62 0.11 26 — 1.50E+10 1.71E+040.059 63 0.38 114 — — — — 64 2.66 138 — — — — 65 0.07 19 0.952 3.00E+091.82E+04 0.078 66 7.74 396 — — — — M_(n)/1000 M_(w)/1000 M_(z)/1000Example (g/mol) (g/mol) (g/mol) M_(w)/M_(n) M_(z)/M_(w)  1 52 187 11183.62 5.97  2 49 198 1405 4.01 7.08  3 52 208 1107 3.98 5.32  4 52 2691842 5.15 6.85  5 54 274 1768 5.03 6.46  6 57 316 1905 5.53 6.02  7 47242 1450 5.14 5.99  8 46 260 1450 5.65 5.58  9 37 230 1071 6.15 4.65 1045 275 1466 6.12 5.32 11 35 237 1367 6.83 5.77 12 48 388 1933 8.04 4.9813 38 337 2012 8.77 5.97 14 59 363  939 6.11 2.59 15 62 350  856 5.672.45 16 63 400  972 6.37 2.43 17 58 379 1023 6.56 2.70 18 36 188 11875.23 6.31 19 20 117  690 5.85 5.87 20 34 225 1593 6.58 7.08 21 33 2281342 6.79 5.89 22 30 152 1032 5.12 6.79 23 25 232 1340 9.23 5.78 24 32264 1323 8.33 5.01 25 44 244 1716 5.57 7.02 26 44 217 1530 4.95 7.06 2744 195 1218 4.39 6.24 28 44 221 1441 5.01 6.52 29 44 208 1226 4.74 5.9030 57 436 2051 7.66 4.70 31 14 141  670 10.04  4.76 32  8 102  40112.45  3.91 35 38 146  557 3.84 3.81 36 40 180  779 4.49 4.33 37 30 1901317 6.34 6.93 38 22 151  876 6.73 5.80 39 37 174  983 4.67 5.63 40 40189 1024 4.63 5.42 41 21 178 1227 8.55 6.90 42 — — — — — 43 39 194 10754.95 5.53 44 45 243 1514 5.45 6.22 45 41 228 1258 5.52 5.51 46 42 2281270 5.44 5.56 47 53 236 1320 4.41 5.61 48 — — — — — 49 50 251 1310 5.055.23 50 37 138  486 3.68 3.53 51 — — — — — 52 — — — — — 53 — — — — — 54— — — — — 56 — — — — — 57 26 239 1303 9.33 5.46 58 — — — — — 59 18 2541397 13.76  5.50 60 10 151  901 14.41  5.97 61 11 152  911 13.29  5.9862 12 160 1085 13.58  6.80 63 — — — — — 64 — — — — — 65 13 176 122013.52  6.94 66 — — — — —

TABLE IV Examples 67-75 and Comparative Example 76-Polymer Properties.MI HLMI Density η₀ τ_(η) CY- Example (g/10 min) (g/10 min) (g/cc)(Pa-sec) (sec) a 67 — — 0.937 2.64E+07 1.59E+02 0.560 68 0.86 25 0.9531.62E+04 5.46E−02 0.321 69 5.8 127 0.961 2.14E+03 7.68E−03 0.356 70 12.4273 0.961 8.14E+02 2.79E-03 0.393 71 — — 0.931 3.36E+17 3.61E+14 0.10572 0.14 12 0.939 6.11E+05 3.00E+00 0.193 73 — 2.6 0.940 4.02E+062.28E+01 0.186 74 0.11 8.6 0.943 1.59E+06 6.97E+00 0.170 75 0.40 240.940 1.20E+05 4.17E−01 0.195 76 0.2 20 0.955 6.07E+05 1.67E+00 0.157M_(n)/1000 M_(w)/1000 M_(z)/1000 Example (g/mol) (g/mol) (g/mol)M_(w)/M_(n) M_(z)/M_(w) 67 49 651 2518  13.16  3.87 68 17 128 416 7.4 3.25 69 12  82 260 6.55 3.19 70  9  67 207 7.03 3.14 71 77 258 1173 3.34 4.54 72 30 161 489 5.25 3.04 73 42 218 659 5.23 3.02 74 28 173 5486.21 3.17 75 21 142 533 6.68 3.77 76 21 145 848 6.99 5.83

TABLE V Average LCB and SCB content in certain molecular weight ranges.Example Example Example 41 60 61 Average SCB's per 1000 total carbonatoms (a) 400,000-600,000 2.4 4.8 13.3 g/mol range (b) 40,000-60,000 1.01.9 6.0 g/mol range Percentage (a)/(b) 240% 253% 222% Average LCB's per1000 total carbon atoms (a) 400,000-600,000 0.0528 0.0410 0.0365 g/molrange (b) 4,000,000-6,000,000 2.9E−7 0.0052 0.0049 g/mol rangePercentage (a)/(b) Too high 788% 745%

The invention is described above with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the above detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. An ethylene polymer having:

a melt index of less than or equal to about 1 g/10 min;

a density in a range from about 0.93 to about 0.965 g/cm³;

a CY-a parameter at 190° C. of less than or equal to about 0.2;

an average number of short chain branches (SCB's) per 1000 total carbonatoms of the polymer in a molecular weight range of 400,000 to 600,000g/mol that is greater (by any amount disclosed herein, e.g., at least25%, at least 50%, at least 75%, at least 100%, at least 125%, etc.)than that in a molecular weight range of 40,000 to 60,000 g/mol; and

an average number of long chain branches (LCB's) per 1000 total carbonatoms of the polymer in a molecular weight range of 400,000 to 600,000g/mol that is greater (by any amount disclosed herein, e.g., at least50%, at least 75%, at least 100%, at least 200%, at least 400%, etc.)than that in a molecular weight range of 4,000,000 to 6,000,000 g/mol.

Aspect 2. The polymer defined in aspect 1, wherein the ethylene polymerhas a melt index (MI) in any range disclosed herein, e.g., less than orequal to about 0.7 g/10 min, less than or equal to about 0.5 g/10 min,less than or equal to about 0.35 g/10 min, less than or equal to about0.25 g/10 min, etc.

Aspect 3. The polymer defined in aspect 1 or 2, wherein the ethylenepolymer has a high load melt index (HLMI) in any range disclosed herein,e.g., from about 2 to about 50 g/10 min, from about 3 to about 40 g/10min, from about 10 to about 45 g/10 min, from about 12 to about 35 g/10min, etc.

Aspect 4. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a ratio of HLMI/MI in any rangedisclosed herein, e.g., from about 80 to about 400, from about 90 toabout 300, from about 100 to about 250, etc.

Aspect 5. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a density in any range disclosedherein, e.g., from about 0.93 to about 0.962 g/cm³, from about 0.93 toabout 0.958 g/cm³, from about 0.935 to about 0.965 g/cm³, from about0.94 to about 0.958 g/cm³, from about 0.95 to about 0.96 g/cm³, etc.

Aspect 6. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a CY-a parameter in any range disclosedherein, e.g., from about 0.02 to about 0.2, from about 0.02 to about0.18, from about 0.02 to about 0.10, from about 0.03 to about 0.15, fromabout 0.04 to about 0.12, etc.

Aspect 7. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a number of short chain branches(SCB's) per 1000 total carbon atoms of the polymer at Mz that is greaterthan at Mw, and/or a number of short chain branches (SCB's) per 1000total carbon atoms of the polymer at Mw that is greater than at Mn,and/or a number of short chain branches (SCB's) per 1000 total carbonatoms of the polymer at Mz that is greater than at Mn (a reverse shortchain branching distribution or increasing comonomer distribution).

Aspect 8. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has an average number of long chainbranches (LCB's) per 1000 total carbon atoms of the polymer in amolecular weight range of 400,000 to 600,000 g/mol in any rangedisclosed herein, e.g., from about 0.015 to about 0.085, from about 0.02to about 0.07, from about 0.03 to about 0.06, etc.

Aspect 9. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer contains from about 0.01 to about 0.08LCB's, from about 0.01 to about 0.06 LCB's, from about 0.02 to about0.06 LCB's, from about 0.02 to about 0.05 LCB's, etc., per 1000 totalcarbon atoms.

Aspect 10. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a ratio of Mw/Mn in any range disclosedherein, e.g., from about 3.5 to about 18, from about 4 to about 16, fromabout 5 to about 15, from about 6 to about 16, etc.

Aspect 11. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a ratio of Mz/Mw in any range disclosedherein, e.g., from about 3.5 to about 10, from about 4 to about 9, fromabout 5 to about 9, from about 5 to about 8, etc.

Aspect 12. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a Mz in any range disclosed herein,e.g., from about 500,000 to about 2,500,000 g/mol, from about 600,000 toabout 2,000,000 g/mol, from about 750,000 to about 2,000,000 g/mol, fromabout 750,000 to about 1,750,000 g/mol, from about 750,000 to about1,500,000 g/mol, etc.

Aspect 13. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a Mw in any range disclosed herein,e.g., from about 100,000 to about 400,000 g/mol, from about 100,000 toabout 300,000 g/mol, from about 100,000 to about 200,000 g/mol, fromabout 150,000 to about 400,000 g/mol, etc.

Aspect 14. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a Mn in any range disclosed herein,e.g., from about 10,000 to about 100,000 g/mol, from about 10,000 toabout 50,000 g/mol, from about 10,000 to about 40,000 g/mol, from about10,000 to about 30,000 g/mol, etc.

Aspect 15. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer has a zero-shear viscosity in any rangedisclosed herein, e.g., from about 1×10⁵ to about 1×10¹⁷ Pa-sec, fromabout 1×10⁶ to about 1×10¹⁶ Pa-sec, from about 1×10⁷ to about 1×10¹³Pa-sec, etc.

Aspect 16. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer is a single reactor product, e.g., not apost-reactor blend of two polymers, for instance, having differentmolecular weight characteristics.

Aspect 17. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer comprises an ethylene/α-olefin copolymerand/or an ethylene homopolymer.

Aspect 18. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer comprises an ethylene/1-butene copolymer,an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, anethylene homopolymer, or any combination thereof.

Aspect 19. The polymer defined in any one of the preceding aspects,wherein the ethylene polymer comprises an ethylene/1-hexene copolymer.

Aspect 20. An article comprising the ethylene polymer defined in any oneof aspects 1-19.

Aspect 21. An article comprising the ethylene polymer defined in any oneof aspects 1-19, wherein the article is an agricultural film, anautomobile part, a bottle, a container for chemicals, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, an outdoor storage product,outdoor play equipment, a pipe, a sheet or tape, a toy, or a trafficbarrier.

Aspect 22. A catalyst composition comprising:

catalyst component I comprising any single atom bridged or two carbonatom bridged metallocene compound disclosed herein with two indenylgroups or an indenyl group and a cyclopentadienyl group;

catalyst component II comprising any single atom bridged metallocenecompound disclosed herein with a fluorenyl group and a cyclopentadienylgroup with an alkenyl substituent;

any activator disclosed herein; and

optionally, any co-catalyst disclosed herein.

Aspect 23. The composition defined in aspect 22, wherein the activatorcomprises an activator-support, an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or any combinationthereof.

Aspect 24. The composition defined in aspect 22, wherein the activatorcomprises an aluminoxane compound.

Aspect 25. The composition defined in aspect 22, wherein the activatorcomprises an organoboron or organoborate compound.

Aspect 26. The composition defined in aspect 22, wherein the activatorcomprises an ionizing ionic compound.

Aspect 27. The composition defined in aspect 22, wherein the activatorcomprises an activator-support, the activator-support comprising anysolid oxide treated with any electron-withdrawing anion disclosedherein.

Aspect 28. The composition defined in aspect 22, wherein the activatorcomprises fluorided alumina, chlorided alumina, bromided alumina,sulfated alumina, fluorided silica-alumina, chlorided silica-alumina,bromided silica-alumina, sulfated silica-alumina, fluoridedsilica-zirconia, chlorided silica-zirconia, bromided silica-zirconia,sulfated silica-zirconia, fluorided silica-titania, fluoridedsilica-coated alumina, fluorided-chlorided silica-coated alumina,sulfated silica-coated alumina, phosphated silica-coated alumina, or anycombination thereof.

Aspect 29. The composition defined in aspect 22, wherein the activatorcomprises fluorided alumina, sulfated alumina, fluorided silica-alumina,sulfated silica-alumina, fluorided silica-coated alumina,fluorided-chlorided silica-coated alumina, sulfated silica-coatedalumina, or any combination thereof.

Aspect 30. The composition defined in aspect 22, wherein the activatorcomprises a fluorided solid oxide and/or a sulfated solid oxide.

Aspect 31. The composition defined in any one of aspects 27-30, whereinthe activator further comprises any metal or metal ion disclosed herein,e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, or any combination thereof.

Aspect 32. The composition defined in any one of aspects 22-31, whereinthe catalyst composition comprises a co-catalyst, e.g., any suitableco-catalyst.

Aspect 33. The composition defined in any one of aspects 22-32, whereinthe co-catalyst comprises any organoaluminum compound disclosed herein.

Aspect 34. The composition defined in aspect 33, wherein theorganoaluminum compound comprises trimethylaluminum, triethylaluminum,triisobutylaluminum, or a combination thereof.

Aspect 35. The composition defined in any one of aspects 27-34, whereinthe catalyst composition comprises catalyst component I, catalystcomponent II, a solid oxide treated with an electron-withdrawing anion,and an organoaluminum compound.

Aspect 36. The composition defined in any one of aspects 22-35, whereincatalyst component I has two unsubstituted indenyl groups.

Aspect 37. The composition defined in any one of aspects 22-36, whereincatalyst component I has a single carbon or silicon bridging atom.

Aspect 38. The composition defined in aspect 37, wherein the carbon orsilicon bridging atom has two substituents independently selected from Hor a C₁ to C₁₈ hydrocarbyl group, e.g.,. a C₁ to C₆ alkyl group.

Aspect 39. The composition defined in any one of aspects 22-36, whereincatalyst component I has a two carbon atom bridge.

Aspect 40. The composition defined in any one of aspects 22-35, whereincatalyst component I has an indenyl group and a cyclopentadienyl group.

Aspect 41. The composition defined in aspect 40, wherein catalystcomponent I has a single carbon or silicon bridging atom.

Aspect 42. The composition defined in aspect 41, wherein the carbon orsilicon bridging atom has two substituents independently selected from Hor a C₁ to C₁₈ hydrocarbyl group, e.g.,. a C₁ to C₆ alkyl group.

Aspect 43. The composition defined in any one of aspects 40-42, whereinat least one of the indenyl group and the cyclopentadienyl group issubstituted.

Aspect 44. The composition defined in any one of aspects 22-43, whereincatalyst component I contains zirconium or titanium.

Aspect 45. The composition defined in any one of aspects 22-44, whereincatalyst component II has a single carbon or silicon bridging atom.

Aspect 46. The composition defined in aspect 45, wherein the carbon orsilicon bridging atom has two substituents independently selected from Hor a C₁ to C₁₈ hydrocarbyl group, e.g., a phenyl group.

Aspect 47. The composition defined in any one of aspects 22-46, whereinthe fluorenyl group is substituted.

Aspect 48. The composition defined in any one of aspects 22-47, whereinthe alkenyl substituent is a C₃ to C₁₈ alkenyl group, e.g., a C₃ to C₈terminal alkenyl group.

Aspect 49. The composition defined in any one of aspects 22-48, whereincatalyst component II contains zirconium, hafnium, or titanium.

Aspect 50. The composition defined in any one of aspects 27-49, whereinthe catalyst composition is substantially free of aluminoxane compounds,organoboron or organoborate compounds, ionizing ionic compounds, orcombinations thereof.

Aspect 51. The composition defined in any one of aspects 22-50, whereina weight ratio of catalyst component Ito catalyst component II in thecatalyst composition is in any range disclosed herein, e.g., from about10:1 to about 1:10, from about 10:1 to about 1:1, from about 5:1 toabout 1:5, from about 5:1 to about 2:1, from about 2:1 to about 1:2,etc.

Aspect 52. The composition defined in any one of aspects 22-51, whereinthe catalyst composition is produced by a process comprising contacting,in any order, catalyst component I, catalyst component II, and theactivator.

Aspect 53. The composition defined in any one of aspects 22-51, whereinthe catalyst composition is produced by a process comprising contacting,in any order, catalyst component I, catalyst component II, theactivator, and the co-catalyst.

Aspect 54. The composition defined in any one of aspects 22-53, whereina catalyst activity of the catalyst composition is in any rangedisclosed herein, e.g., from about 500 to about 5000, from about 750 toabout 4000, from about 1000 to about 3500 grams, etc., of ethylenepolymer per gram of activator-support per hour, under slurrypolymerization conditions, with a triisobutylaluminum co-catalyst, usingisobutane as a diluent, and with a polymerization temperature of 90° C.and a reactor pressure of 400 psig.

Aspect 55. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of aspects 22-54with an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer.

Aspect 56. The process defined in aspect 55, wherein the olefin monomercomprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀ olefin.

Aspect 57. The process defined in aspect 55 or 56, wherein the olefinmonomer and the olefin comonomer independently comprise a C₂-C₂₀alpha-olefin.

Aspect 58. The process defined in any one of aspects 55-57, wherein theolefin monomer comprises ethylene.

Aspect 59. The process defined in any one of aspects 55-58, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Aspect 60. The process defined in any one of aspects 55-59, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 61. The process defined in any one of aspects 55-57, wherein theolefin monomer comprises propylene.

Aspect 62. The process defined in any one of aspects 55-61, wherein thepolymerization reactor system comprises a batch reactor, a slurryreactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Aspect 63. The process defined in any one of aspects 55-62, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Aspect 64. The process defined in any one of aspects 55-63, wherein thepolymerization reactor system comprises a loop slurry reactor.

Aspect 65. The process defined in any one of aspects 55-64, wherein thepolymerization reactor system comprises a single reactor.

Aspect 66. The process defined in any one of aspects 55-64, wherein thepolymerization reactor system comprises 2 reactors.

Aspect 67. The process defined in any one of aspects 55-64, wherein thepolymerization reactor system comprises more than 2 reactors.

Aspect 68. The process defined in any one of aspects 55-67, wherein theolefin polymer comprises any olefin polymer disclosed herein.

Aspect 69. The process defined in any one of aspects 55-60 and 62-68,wherein the olefin polymer comprises an ethylene homopolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or anethylene/1-octene copolymer.

Aspect 70. The process defined in any one of aspects 55-60 and 62-68,wherein the olefin polymer comprises an ethylene/1-hexene copolymer.

Aspect 71. The process defined in any one of aspects 55-57 and 61-68,wherein the olefin polymer comprises a polypropylene homopolymer or apropylene-based copolymer.

Aspect 72. The process defined in any one of aspects 55-71, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 60° C. to about 120° C. and a reaction pressure ina range from about 200 to about 1000 psig (about 1.4 to about 6.9 MPa).

Aspect 73. The process defined in any one of aspects 55-72, wherein thepolymerization conditions are substantially constant, e.g., for aparticular polymer grade.

Aspect 74. The process defined in any one of aspects 55-73, wherein nohydrogen is added to the polymerization reactor system.

Aspect 75. The process defined in any one of aspects 55-73, whereinhydrogen is added to the polymerization reactor system.

Aspect 76. The process defined in any one of aspects 55-75, wherein theolefin polymer produced is defined in any one of aspects 1-19.

Aspect 77. An olefin polymer produced by the olefin polymerizationprocess defined in any one of aspects 55-75.

Aspect 78. An ethylene polymer defined in any one of aspects 1-19produced by the process defined in any one of aspects 55-75.

Aspect 79. An article comprising the polymer defined in any one ofaspects 77-78.

Aspect 80. A method or forming or preparing an article of manufacturecomprising an olefin polymer, the method comprising (i) performing theolefin polymerization process defined in any one of aspects 55-75 toproduce an olefin polymer (e.g., the ethylene polymer of any one ofaspects 1-19), and (ii) forming the article of manufacture comprisingthe olefin polymer, e.g., via any technique disclosed herein.

We claim:
 1. An ethylene polymer having: a melt index of less than orequal to about 1 g/10 min; a density in a range from about 0.93 to about0.965 g/cm³; a CY-a parameter at 190° C. of less than or equal to about0.2; an average number of short chain branches (SCB's) per 1000 totalcarbon atoms of the polymer in a molecular weight range of 400,000 to600,000 g/mol that is greater than that in a molecular weight range of40,000 to 60,000 g/mol; and an average number of long chain branches(LCB's) per 1000 total carbon atoms of the polymer in a molecular weightrange of 400,000 to 600,000 g/mol that is greater than that in amolecular weight range of 4,000,000 to 6,000,000 g/mol.
 2. An article ofmanufacture comprising the polymer of claim
 1. 3. The polymer of claim1, wherein: the average number of SCB's per 1000 total carbon atoms ofthe polymer in the molecular weight range of 400,000 to 600,000 g/mol isat least 50% greater than that in the molecular weight range of 40,000to 60,000 g/mol; and the average number of LCB's per 1000 total carbonatoms of the polymer in the molecular weight range of 400,000 to 600,000g/mol is at least 100% greater than that in the molecular weight rangeof 4,000,000 to 6,000,000 g/mol.
 4. The polymer of claim 1, wherein: themelt index is less than or equal to about 0.5 g/10 min; the density isin a range from about 0.93 to about 0.958 g/cm³; and the CY-a parameterat 190° C. is in a range from about 0.03 to about 0.15.
 5. The polymerof claim 4, wherein the ethylene polymer comprises an ethylene/1-butenecopolymer, an ethylene/1-hexene copolymer, an ethylene/1-octenecopolymer, or a combination thereof.
 6. The polymer of claim 5, whereinthe ethylene polymer has a HLMI in a range from about 10 to about 45g/10 min.
 7. The polymer of claim 1, wherein the ethylene polymer has: aratio of M_(w)/M_(n) in a range from about 3.5 to about 18; and a ratioof M_(z)/M_(w) in a range from about 3.5 to about
 10. 8. The polymer ofclaim 1, wherein the ethylene polymer has: a M_(n) in a range from about10,000 to about 100,000 g/mol; a M_(w) in a range from about 100,000 toabout 400,000 g/mol; and a M_(z) in a range from about 500,000 to about2,500,000 g/mol.
 9. The polymer of claim 1, wherein the ethylene polymercontains from about 0.01 to about 0.06 LCB's per 1000 total carbonatoms.
 10. The polymer of claim 1, wherein the ethylene polymer has anaverage number of LCB's in a range from about 0.015 to about 0.085 LCB'sper 1000 total carbon atoms in the molecular weight range of 400,000 to600,000 g/mol.
 11. The polymer of claim 1, wherein the ethylene polymerhas a zero-shear viscosity in a range from about 1×10⁶ to about 1×10¹⁶Pa-sec at 190° C.
 12. The polymer of claim 1, wherein the ethylenepolymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, an ethylene/1-octene copolymer, or a combination thereof. 13.The polymer of claim 12, wherein the ethylene polymer has: a ratio ofM_(w)/M_(n) in a range from about 6 to about 16; and a ratio ofM_(z)/M_(w) in a range from about 5 to about
 8. 14. The polymer of claim12, wherein the ethylene polymer has: a M_(n) in a range from about10,000 to about 40,000 g/mol; a M_(w) in a range from about 100,000 toabout 300,000 g/mol; a M_(z) in a range from about 750,000 to about1,500,000 g/mol; and an average number of LCB's in a range from about0.02 to about 0.07 LCB's per 1000 total carbon atoms in the molecularweight range of 400,000 to 600,000 g/mol.
 15. An article of manufacturecomprising the polymer of claim
 14. 16. The polymer of claim 12,wherein: the average number of SCB's per 1000 total carbon atoms of thepolymer in the molecular weight range of 400,000 to 600,000 g/mol is atleast 75% greater than that in the molecular weight range of 40,000 to60,000 g/mol; and the average number of LCB's per 1000 total carbonatoms of the polymer in the molecular weight range of 400,000 to 600,000g/mol is at least 200% greater than that in the molecular weight rangeof 4,000,000 to 6,000,000 g/mol.
 17. An olefin polymerization process,the process comprising contacting a catalyst composition with an olefinmonomer and an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein: thecatalyst composition comprises: catalyst component I comprising a singleatom bridged or two carbon atom bridged metallocene compound with twoindenyl groups or an indenyl group and a cyclopentadienyl group;catalyst component II comprising a single atom bridged metallocenecompound with a fluorenyl group and a cyclopentadienyl group with analkenyl substituent; an activator; and optionally, a co-catalyst; andthe olefin polymer is characterized by: a melt index of less than orequal to about 1 g/10 min; a density in a range from about 0.93 to about0.965 g/cm³; a CY-a parameter at 190° C. of less than or equal to about0.2; an average number of short chain branches (SCB's) per 1000 totalcarbon atoms of the polymer in a molecular weight range of 400,000 to600,000 g/mol that is greater than that in a molecular weight range of40,000 to 60,000 g/mol; and an average number of long chain branches(LCB's) per 1000 total carbon atoms of the polymer in a molecular weightrange of 400,000 to 600,000 g/mol that is greater than that in amolecular weight range of 4,000,000 to 6,000,000 g/mol.
 18. The processof claim 17, wherein: the olefin monomer comprises ethylene; the olefincomonomer comprises a C₃-C₁₀ alpha-olefin; and the polymerizationreactor system comprises a slurry reactor, a gas-phase reactor, asolution reactor, or a combination thereof.
 19. The process of claim 17,wherein: the catalyst composition is contacted with ethylene and anolefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixturethereof; the activator comprises an activator-support, an aluminoxanecompound, an organoboron or organoborate compound, an ionizing ioniccompound, or any combination thereof; the catalyst composition comprisesan organoaluminum co-catalyst; and a weight ratio of catalyst componentIto catalyst component II in the catalyst composition is in a range fromabout 5:1 to about 1:5.
 20. The process of claim 19, wherein: catalystcomponent I comprises a two carbon atom bridged metallocene compoundwith two unsubstituted indenyl groups; and catalyst component IIcomprises a single carbon atom bridged metallocene compound with asubstituted fluorenyl group and a cyclopentadienyl group with a C₃ to C₈terminal alkenyl substituent.